JPH07311461A - Water-soluble colored photosensitive resin composition - Google Patents

Abstract

PURPOSE:To obtain a water-soluble colored photosensitive resin compsn. for forming the colored layer of a color filter contg. no heavy metal or org. solvent, developable wit.h an aq. developer and giving a colored pattern with high resolution even by proximity exposure. CONSTITUTION:This water-soluble colored photosensitive resin compsn. contains a water-soluble resin, a crosslinking agent contg. a water-soluble azido compd. and a colorant. The water-soluble resin contains a polymer using at least one kind of acrylamide monomer selected from among alpha-substitution products of acrylamide, N-monosubstitution products of acrylamide, N,N-clisubstitution products of acrylamide and N-monosubstitution products of methacrylamide.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-soluble colored photosensitive resin composition colored with a coloring agent, and particularly to a water-soluble coloring used for forming a coloring pattern of a color filter used in a color liquid crystal display device or the like. It relates to a photosensitive resin composition.

[0002]

2. Description of the Related Art A transparent substrate such as glass or plastic is provided with a colored layer such as a resin or a vapor deposition film colored with a dye or a pigment,
A color filter with a transparent electrode formed on it is
A color liquid crystal display device in which a certain gap is provided with respect to a substrate on which a transparent electrode is formed and a twisted nematic liquid crystal is enclosed in the gap is widely used in televisions, laptop personal computers, and the like.

The color filter used here is
Light-shielding layer (black matrix) that partitions adjacent pixels on a transparent substrate and improves the contrast of the displayed image
Is formed by applying electroless plating to a resin or resin relief in which chrome or a black pigment is dispersed, and then a colored layer is formed by exposing and developing a photosensitive resin, etc. Method (dyeing method), a method of forming a pattern of a photosensitive resin colored with a pigment by photolithography (pigment dispersion method), a method of transferring a colored ink by an intaglio offset method, and a method of curing an ink layer by heat ( (Printing method) or the like, and if necessary, provide a transparent protective layer for improving heat resistance, chemical resistance, etc.
In the case of the active matrix system by vapor deposition or sputtering of TO etc., the common electrode, STN
In the case of the method, it is manufactured by forming a striped electrode.

In the above pigment dispersion method, a colored photosensitive resin composition colored with a coloring agent such as a pigment is applied onto a substrate, exposed in a desired pattern, and then developed to develop a patterned colored relief. And a colored layer is formed by repeating this step for a desired hue such as red, green and blue. The photosensitive resin used in such a colored photosensitive resin composition is a water-soluble photosensitive resin. In JP-A-60-129738, it is proposed to use a polyvinyl alcohol resin (hereinafter referred to as PVA-SbQ) having photosensitivity by a stilbazolium group, and a diluting solvent such as a glycol ether-based organic resin is used. As an organic solvent type using a solvent, a photosensitive acrylic resin, a photosensitive polyamide resin and the like are known.

[0005]

However, in a photosensitive resin composition using an organic solvent-based photosensitive resin, the risk of pregnancy disorders due to the contained organic solvent has been pointed out, and safety is a problem. Has become. Further, the photosensitive resin composition using an organic solvent-based developer in the phenomenon treatment has problems in workability and safety.

Further, in the above-mentioned photosensitive resin composition using PVA-SbQ, since both the diluting solvent and the developing solution are water-based, there is no problem in workability and safety, but the proximity ( Proximity) had a problem that sufficient resolution could not be obtained. The cause of this is
Due to the swelling property of PVA, thickening of the pattern during the development process,
Deformation and sagging of the pattern edge may occur.

The present invention has been made in view of the above-mentioned circumstances, and it is possible to perform water development with a water-based developer without containing a heavy metal or an organic solvent and to have high resolution even in proximity exposure. An object of the present invention is to provide a water-soluble colored photosensitive resin composition for forming a colored layer of a color filter capable of obtaining a colored pattern.

[0008]

In order to achieve such an object, the water-soluble colored photosensitive resin composition of the present invention comprises an α-substituted acrylamide, an N-monosubstituted acrylamide, and an N-substituted acrylamide. A water-soluble resin having a polymer using at least one monomer selected from the group of acrylamide monomers consisting of N-di-substituted compounds and N-mono-substituted compounds of methacrylamide, and a water-soluble azide compound It was configured to include a crosslinking agent and a coloring agent.

Since the water-soluble resin contains a water-soluble resin having a polymer using at least one of the above-mentioned acrylamide type monomers, the development can be carried out with water, and the patterning without using an organic solvent is possible. The process becomes possible, and since the crosslinking agent containing a water-soluble azide compound is contained as a crosslinking agent, heavy metals, organic solvents, etc. are not contained in the waste liquid and the development waste liquid of the water-soluble photosensitive resin composition, and the waste water is drained. Processing becomes easier, and sufficient resolution can be obtained even in proximity exposure.

The water-soluble colored photosensitive resin composition of the present invention comprises
As described above, it contains the water-soluble resin, the cross-linking agent, and the colorant. Next, each component will be described.

First, the water-soluble resin which constitutes the water-soluble colored photosensitive resin composition of the present invention includes α-substituted acrylamide, N-monosubstituted acrylamide, N, N-disubstituted acrylamide and methacrylic It has a polymer using at least one kind of monomer selected from the group of acrylamide monomers consisting of N-mono-substituted amides.

Methacrylamide (= α.methylacrylamide), α.phenylacrylamide and the like can be mentioned as α-substituted acrylamides which can be used in the above polymer. Further, N-monosubstituted acrylamides include N-isopropylacrylamide and N-isopropylacrylamide.
Examples thereof include -t-octyl acrylamide, N-methylol acrylamide, N, N'-methylene bis (acrylamide), N-diacetone acrylamide, N- (n-butoxymethyl) acrylamide, N, N-dimethylaminopropyl acrylamide. Examples of N, N-disubstituted acrylamides include N, N-dimethylacrylamide, N, N-diethylacrylamide and acrylmorpholine. Furthermore, examples of the N-mono-substituted methacrylamide include N-methyl methacrylamide and the like.

The water-soluble resin constituting the water-soluble colored photosensitive resin composition of the present invention is a polymer using at least one kind of the above-mentioned acrylamide type monomer, and is either a copolymer or a homopolymer. May be When the water-soluble resin is a copolymer, the monomer may be a combination of two or more of the above-mentioned acrylamide-based monomers, or a combination of the above-mentioned acrylamide-based monomers and other monomers. Other monomers that can be copolymerized with the above acrylamide-based monomer include acrylonitrile, acrylamide,
Examples thereof include water-soluble monomers such as acrylic acid and water-insoluble monomers such as styrene, vinyl chloride and methyl methacrylate. The rate at which these monomers to be copolymerized are introduced into the copolymer depends largely on the combination of the monomers, but if the rate of introduction of other monomers becomes too high, crosslinking due to the acrylamide monomer will occur. It is desirable that the amount of the other monomer with respect to the acrylamide-based monomer is 60% by weight or less, preferably 20% by weight or less, because the property of being easy and having good adhesion to the substrate is deteriorated. The copolymerization of the above-mentioned acrylamide-based monomer and other monomer can be carried out by a known method such as radical polymerization.

When the water-soluble resin is a homopolymer, the acrylamide-based monomers preferably used in terms of water-solubility are methacrylamide, N-methylacrylamide, N-ethylacrylamide, N-isopropylacrylamide, N, N. -Dimethylacrylamide, N, N
-Although it is limited to diethyl acrylamide, N, N-dimethylaminopropyl acrylamide, etc., the characteristics of acrylamide, such as easy crosslinking, high water absorption, good adhesion, and hardness, are more clearly defined. It is preferably added to the water-soluble resin.

Further, as the water-soluble resin constituting the water-soluble colored photosensitive resin composition of the present invention, a mixture of the above copolymer or homopolymer and another water-soluble polymer can be used. . Examples of other water-soluble polymers include gelatin, casein, glue, gum arabic, shellac, natural polymers such as ovalbumin, carboxymethyl cellulose, polyvinyl alcohol, polyacrylic acid, polyacrylamide, polyvinylpyrrolidone, polyethylene oxide, and anhydrous. Mention may be made of synthetic polymers such as maleic acid copolymers, or copolymers thereof. In this case, the proportion of the other water-soluble polymer in the water-soluble resin is desirably 60% by weight or less, preferably 20% by weight or less. If this ratio exceeds 60% by weight, the properties of the other water-soluble resin will be more dominant than the properties of the water-soluble resin containing the acrylamide monomer, and the properties of the water-soluble resin containing the acrylamide monomer will be sufficiently expressed. Not desirable.

The degree of polymerization of these water-soluble resins is 50 to 1
It is preferably about 0000. If the degree of polymerization is less than 50, sufficient sensitivity cannot be obtained, and if it exceeds 10,000, the viscosity of the water-soluble resin becomes extremely large, resulting in poor coating properties and sufficient resolution when photocrosslinked. Can't get

The water-soluble azide compound used as the cross-linking agent constituting the water-soluble colored photosensitive resin composition of the present invention is
4,4'-diazidostilbene-2,2'-disulfonic acid and its disodium salt, dipotassium salt, or its organic amine salt (as the organic amine, 3 hydroxypropylamine, ethoxyethylamine, diethanolamine, triethylamine, Tetramethylammonium, tetraethylammonium, etc.) and the like.

The water-soluble colored photosensitive resin composition of the present invention comprises
The above water-soluble resin and crosslinking agent are dissolved in water. Then, the total amount of the water-soluble resin solid content and the cross-linking agent solid content in the water-soluble photosensitive resin composition can be determined according to the coating device used. For example, when a spin coater is used, the total amount of the water-soluble resin solid content and the crosslinking agent solid content is 1 to 10% by weight of the water-soluble photosensitive resin composition.
A degree is preferable. If this ratio is less than 1% by weight, a sufficient coating film thickness cannot be obtained because the solid content ratio is too low. On the other hand, if it exceeds 10% by weight, the viscosity of the water-soluble colored photosensitive resin composition is too high, so that the coating suitability by the spin coating method is deteriorated and a uniform film thickness cannot be obtained, which is not preferable. The ratio of the cross-linking agent to the water-soluble resin is 5 to
It is preferably about 20% by weight. If this ratio is less than 5% by weight, the sensitivity of the water-soluble photosensitive resin composition will be insufficient, and if it exceeds 20% by weight, film peeling will occur during development, which is not preferable. It is presumed that this film peeling occurred because the adhesion between the substrate and the water-soluble colored photosensitive resin composition decreased.

In addition to the above-mentioned water-soluble resin and crosslinking agent, the water-soluble colored photosensitive resin composition of the present invention may further contain additives such as a surfactant and a silane coupling agent, if necessary. May be.

The colorant used in the present invention includes
Although either a dye or a pigment can be used, it is preferable to use the pigment in terms of reliability such as heat resistance and light resistance.

As the pigment, a color index (C.
I.) Numbers include: First, as a red pigment, CI Pigment Red 48, 97, 1
22, 123, 144, 149, 166, 168, 17
7, 178, 180, 187, 190, 192, 20
8,209,215,216,217,220,22
3, 224, 226, 227, 228, 240 and the like. In addition, as a green pigment, CI Pigment Green
7, 36 and the like. In addition, as a blue pigment, CI
Pigment Blue 15, 15: 1, 15: 3, 15: 4,
15: 6, 22, 60, 64 and the like. The above-mentioned pigments can be used alone or in combination in the water-soluble colored photosensitive resin composition. In addition to the above three primary color pigments, yellow,
Pigments such as purple and orange can also be used. For example,
CI Pigment Yellow 17, 24, 8 as a yellow pigment
3, 86, 93, 94, 108, 109, 110, 11
7, 125, 128, 137, 138, 147, 15
3, 154, 166, 168 and the like. As a purple pigment, CI Pigment Violet 19, 23, 2
9, 30, 32, 37, 40, 50 and the like, and as the orange pigment, CI Pigment Orange 13, 36,
43, 51, 55, 59, 61, 64, 65 and the like.

When the above-mentioned coloring agent is added to the water-soluble colored photosensitive resin composition of the present invention, the addition amount of the coloring agent is about 10 to 150% by weight based on the total amount of the water-soluble resin and the crosslinking agent. preferable. Further, the added colorant needs to be sufficiently dispersed in the water-soluble colored photosensitive resin composition. The dispersion method is not particularly limited, but for example, a stirring method, a ball mill method, a three-roll method or the like can be used.

The particle size of the colorant used is preferably 1 μm or less in view of the transparency of the water-soluble colored photosensitive resin composition containing the colorant and the dispersion stability of the colorant. Further, a dispersion stabilizer may be added to enhance the dispersion stability of the colorant.

[0024]

EXAMPLES The present invention will be described below based on examples. Examples 1 to 3 As the water-soluble resin, a copolymer of one kind of acrylamide-based monomer (N-mono-substituted acrylamide) and another monomer is used, and a colorant is added to The water-soluble colored photosensitive resin compositions (Examples 1 to 3) having the above composition were prepared. (Water-soluble colored photosensitive resin composition of Example 1) N-diacetone acrylamide / acrylamide copolymer (manufactured by Toyo Gosei Co., Ltd.) ... 2.7 parts by weight 4,4'-diazidostilbene- 2,2'-disulfonic acid disodium salt: 0.3 parts by weight of water: 97 parts by weight of a silane coupling agent (KBM-603, manufactured by Shin-Etsu Chemical Co., Ltd.): 0.03 parts by weight: Anthraquinone colorant Red CIPigment Red 208 ... 2.4 parts by weight-Colorant Disazo Yellow CIPigment Yellow 83 ... 0.6 parts by weight (water-soluble colored photosensitive resin composition of Example 2) -N-diacetone acrylamide / acrylamide copolymer ( Toyo Gosei Co., Ltd.) 2.7 parts by weight 4,4'-diazidostilbene-2,2'-disulfonic acid disodium salt ... 0.3 parts by weight water ... 97 parts by weight Silaneca Pulling agent (KBM-603, manufactured by Shin-Etsu Chemical Co., Ltd.) ... 0.03 parts by weight-Colorant phthalocyanine green CIPigment Green 36 ... 2.3 parts by weight-Colorant disazo yellow CIPigment Yellow 83 ... 0.7 parts by weight Water-soluble colored photosensitive resin composition of Example 3) N-diacetone acrylamide / acrylamide copolymer (manufactured by Toyo Gosei Co., Ltd.) ... 2.7 parts by weight 4,4'-diazidostilbene-2, 2'-disulfonic acid disodium salt ... 0.3 parts by weight water ... 97 parts by weight Silane coupling agent (KBM-603 manufactured by Shin-Etsu Chemical Co., Ltd.) ... 0.03 parts by weight Colorant Phthalocyanine Blue CIPigment Blue 15: 3/15: 4 Mixture ... 1.7 parts by weight Colorant Dioxazine Violet CIPigment Violet 23 ... 1.3 parts by weight Examples 4 to 6 As water-soluble resins, One of the crylamide monomers (N, N-disubstituted acrylamide)
Water-soluble colored photosensitive resin composition having the following composition by using a homopolymer of
6) was prepared. (Water-soluble colored photosensitive resin composition of Example 4) N, N-dimethylacrylamide polymer (manufactured by Kojin Co., Ltd.) ... 4.5 parts by weight 4,4'-diazidostilbene-2,2 ′ -Disulfonic acid disodium salt: 0.5 part by weight, water: 95 parts by weight, surfactant (LT-221 manufactured by NOF CORPORATION), 0.2 part by weight, silane coupling agent (Shin-Etsu Chemical Co., Ltd. KBM-603) ... 0.25 parts by weight-Colorant anthraquinone red CIPigment Red 177 ... 3.8 parts by weight-Colorant disazo yellow CIPigment Yellow 83 ... 0.7 parts by weight (water-soluble coloring of Example 5) Photosensitive resin composition) N, N-dimethylacrylamide polymer (manufactured by Kojin Co., Ltd.) 4.5 parts by weight 4,4'-diazidostilbene-2,2'-disulfonic acid disodium salt 0.5 parts by weight Water ... 95 parts by weight Activator (LT-221 manufactured by NOF CORPORATION)… 0.2 parts by weight ・ Silane coupling agent (KBM-603 manufactured by Shin-Etsu Chemical Co., Ltd.)… 0.25 part by weight ・ Colorant Phthalocyanine Green CIPigment Green 36 ... 3.4 parts by weight-Colorant Disazo Yellow CIPigment Yellow 83 ... 1.1 parts by weight (water-soluble colored photosensitive resin composition of Example 6) -N, N-dimethylacrylamide polymer (manufactured by Kojin Co., Ltd.) ) 4.5 parts by weight 4,4'-diazidostilbene-2,2'-disulfonic acid disodium salt ... 0.5 parts by weight water ... 95 parts by weight Surfactant (manufactured by NOF Corporation) LT-221) 0.2 parts by weight Silane coupling agent (KBM-603, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.25 parts by weight Colorant Phthalocyanine Blue CIPigment Blue 15: 6 4.2 parts by weight Colorant di Kisa Jin violet CI Pigment Violet 23 ... 0.3 parts by weight Comparative Examples 1 to 3 water soluble colored photosensitive resin composition of the following composition (Comparative Example 1
3) was prepared. (Water-soluble colored photosensitive resin composition of Comparative Example 1) -Polyvinyl alcohol derivative in which 1.2 mol% of stilbazolium group structural unit was introduced to polyvinyl alcohol structural unit ... 4.5 parts by weight-Water ... 95.5 Parts by weight-colorant anthraquinone red CIPigment Red 177 ... 3.8 parts by weight-colorant disazo yellow CIPigment Yellow 83 ... 0.7 parts by weight (water-soluble colored photosensitive resin composition of Comparative Example 2) -polyvinyl alcohol constituent unit To the polyvinyl alcohol derivative in which 1.2 mol% of the stilbazolium group structural unit was introduced, 4.5 parts by weight, water, 95.5 parts by weight, colorant phthalocyanine green CIPigment Green 36, 3.4 parts by weight, colorant Disazo Yellow CIPigment Yellow 83 ... 1.1 parts by weight (water-soluble colored photosensitive resin composition of Comparative Example 3) 3. Polyvinyl alcohol derivative in which 1.2 mol% of the stilbazolium group structural unit is introduced with respect to the rucohol structural unit 4.5 parts by weight Water 95.5 parts by weight Colorant Phthalocyanine Blue CIPigment Blue 15: 6. 2 parts by weight Colorant dioxazine violet CIPigment Violet 23 ... 0.3 parts by weight The water-soluble colored photosensitive resin compositions (Examples 1 to 6 and Comparative Examples 1 to 3) prepared as described above were spin-coated. 7059 glass (thickness = 1.1 mm) manufactured by Corning Co., Ltd. as a transparent substrate by the method, respectively, at 70 ° C. for 5
A colored photosensitive resin layer (thickness = 1.2 μm) was formed by pre-baking under the condition of minutes.

Next, an exposure amount of 20 mJ / cm ² was applied to the above colored photosensitive resin layer through a photomask having a line & space pattern using a proximity exposure machine equipped with a 2 kW ultra high pressure mercury lamp. It was The proximity gap amount was set to 100 μm. Then, after performing spray development for 45 seconds using water at room temperature, post baking was performed at 100 ° C. for 5 minutes to form a fine pattern. The resolution (line & space) of the obtained fine pattern is shown in Table 1 below together with the optimum exposure amount.

Further, the spectral transmittances of Examples 1 to 6 were measured, and their chromaticity coordinates (x, y, Y) were determined, and the results are shown in Table 2 below.

[0027]

[Table 1]

[0028]

[Table 2] As shown in Table 1, Examples 1 to 6 have a resolution of 20 μm.
It was m or less, had an extremely high resolution even in proximity exposure, and could be sufficiently used as a water-soluble colored photosensitive resin composition for forming a fine colored pattern such as a color filter.

On the other hand, Comparative Examples 1 to 3 are capable of forming fine patterns, but have a resolution of 30 μm or more and are used as water-soluble colored photosensitive resin compositions for forming fine colored patterns such as color filters. Was not enough for.

[0030]

As described in detail above, the water-soluble colored photosensitive resin composition of the present invention contains no organic solvent or heavy metal, can be developed with water, and is harmful to heavy metals, organic solvents, etc. in the waste liquid. Since no substance is contained, the wastewater treatment is facilitated, the cost for forming the fine colored pattern can be reduced, and the resolution in proximity exposure is high, and the fine colored pattern with high dimensional accuracy can be formed.

Claims (5)

[Claims] 1. A group of acrylamide monomers selected from α-substituted acrylamides, N-monosubstituted acrylamides, N, N-disubstituted acrylamides and N-monosubstituted methacrylamides. A water-soluble colored photosensitive resin composition comprising a water-soluble resin having a polymer using at least one monomer, a crosslinking agent having a water-soluble azide compound, and a colorant. 2. The water-soluble colored photosensitive resin composition according to claim 1, wherein the polymer is a copolymer using two or more kinds of monomers. 3. The water-soluble colored photosensitive resin composition according to claim 2, wherein the copolymer is a copolymer using only the acrylamide-based monomer. 4. The water-soluble colored photosensitive resin composition according to claim 1, wherein the polymer is a homopolymer using one kind of monomer. 5. The water-soluble colored photosensitive resin composition according to any one of claims 1 to 4, wherein the colorant is a pigment.